CN101214395A - Inorganic material surface biological method - Google Patents
Inorganic material surface biological method Download PDFInfo
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- CN101214395A CN101214395A CNA2008100451034A CN200810045103A CN101214395A CN 101214395 A CN101214395 A CN 101214395A CN A2008100451034 A CNA2008100451034 A CN A2008100451034A CN 200810045103 A CN200810045103 A CN 200810045103A CN 101214395 A CN101214395 A CN 101214395A
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Abstract
A method of biolization to the surface of inorganic material includes the following steps: the surface is spattered to form a tantalum oxide or a titanium oxide thin film; and then the inorganic material is put in a plasma immersion ion implantation device; after vacuumization, hydrogen, water vapour or ammonia is fed in, with gas pressure 0.05 to 50 Pa; the radio frequency discharge power is 200 to 1200W; the range value of the loaded pulse high-voltage power is 1KV to 100KV, the frequency is 50 to 40000HZ, and the duty ratio is 3 percent to 80 percent; the heating temperature is 20 to 500 DEG C; the treatment time is 0.1 to 5 hours; finally, the inorganic material is put into 10 to 100mg/mL albumin or heparin solution to be soaked for 2 to 48 hours under 20 to 40 DEG C soaking temperature. The method does not damage the activity of the biomolecule and the protein; the prepared inorganic material with biolized surface has good anti-coagulability, is used for medical blood vessel scaffolds and artificial heart valves, and can greatly improve the product performance.
Description
Technical field
The present invention relates to a kind of method of material surface bioid, relate in particular to a kind of method of inorganic material surface biological.
Background technology
The bio-medical material that is used for manufacture of intraocular heart, artificial valve, artificial lung, intravascular stent and artificial blood vessel etc. is called the biomaterial that contacts with blood, it should have good anticoagulant property, could realize both being suppressed at activation and the hematoblastic gathering and the distortion of material surface thrombin, can select to adsorb some plasma protein again, thus the formation of anti-tampon.In recent years, the bioid of polymeric biomaterial is that anticoagulation research has obtained very big progress, its main way is that modification and modification are carried out in the polymeric biomaterial surface of function admirable, by changing the surface texture of material, pattern, hydrophilic and hydrophobic, charge, surface energy etc., the guiding biomolecule is in the selective absorption of material surface, in addition, researcher also adopts the biological active substances that fixedly has anticoagulation function at material surface, as heparin, hirudin, albumin etc., development has the macromolecular material of surface bioactive, by the approach of bio-identification, better improve the anticoagulation function of polymeric biomaterial.
By contrast, be that anticoagulation research is less to the bioid of inorganic bio, this mainly is because inorganic biomaterial for medical purpose surface lacks organo-functional group, is difficult in directly biomolecule such as fixing heparin, albumin, thrombosis modified protein of its surface.The bioid method of existing inorganic material is: adopt the method for coupling agent such as gamma-aminopropyl-triethoxy-silane (APTES) or static self assembly to fix, apply biomolecule such as heparin, albumin, thrombosis modified protein.Through after such modification, may cause that the activity of biomolecule weakens, and biological coating and material surface between adhesion a little less than, the bioid weak effect.
Summary of the invention
Purpose of the present invention just provides a kind of method of inorganic material surface biological, this method is not damaged biomolecule and proteic activity, inorganic material surface has excellent anticoagulation function, is used for medical blood vessel support and Cardiac valve prosthesis, can increase substantially properties of product.
The present invention realizes its goal of the invention, and the technical scheme that is adopted is: a kind of method of inorganic material surface biological the steps include:
A, sputter coating: generate tantalum oxide or thin film of titanium oxide in the inorganic material surface sputter;
The generation of B, hydroxyl or primary amino radical:
Inorganic material after A step handled places on the sample platform of vacuum chamber of plasma immersion ion injection device, behind the evacuation, feeds hydrogen or water vapour, and pressure is 0.05～50 handkerchief; Radio-frequency discharge power is 200～1200W; Inorganic material loading pulse high voltage power supply amplitude is 1KV～100KV, 50～40000 hertz of frequencies, dutycycle 3%～80%; Inorganic material heating-up temperature 20～500 degree; In 0.1～5 hour processing time, promptly generate hydroxyl at inorganic material surface;
Inorganic material after perhaps A step being handled places on the sample platform of vacuum chamber of plasma immersion ion injection device, behind the evacuation, feeds ammonia, and pressure is 0.05～50 handkerchief; Radio-frequency discharge power is 200～1200W; Inorganic material loading pulse high voltage power supply amplitude is 1KV～100KV, 50～40000 hertz of frequencies, dutycycle 3%～80%, and inorganic material heating-up temperature 20～500 degree in 0.1～5 hour processing time, promptly generate primary amino radical at inorganic material surface;
C, covalence graft biomolecule: the inorganic material after B step handled, put into albumin or heparin solution soaks, the concentration of albumin or heparin solution is 10～100mg/mL, 20～40 ℃ of soaking temperatures, 2～48 hours time.
When the above-mentioned B step hydroxyl or the generation of primary amino radical, more excellent process conditions are:
The pressure that feeds hydrogen or water vapour is 0.5～40 handkerchief; Radio-frequency discharge power is 300～1000W; Inorganic material loading pulse high voltage power supply amplitude is 5KV～80KV, 50～10000 hertz of frequencies, dutycycle 3%～20%; Inorganic material heating-up temperature 50～400 degree; 1～4 hour processing time;
The pressure that feeds ammonia is 0.5～40 handkerchief; Radio-frequency discharge power is 300～1000W; Inorganic material loading pulse high voltage power supply amplitude is 5KV～80KV, 50～10000 hertz of frequencies, dutycycle 3%～20%; Inorganic material heating-up temperature 50～400 degree; 1～4 hour processing time.
Compared with prior art, the invention has the beneficial effects as follows:
Studies show that, behind inorganic material such as titanium implant implant into body, under liquid environment, surface film oxide generation aquation at first, make the skin of oxide-film be rich in hydroxyl or primary amino radical, subsequently, the biomacromolecule of body biologically active has been adsorbed onto the oxide-film surface of being rich in hydroxyl or primary amino radical selectively, thereby produces the biomacromolecule of biologically active on the surface of titanium implant.Under the mediation of this kind biomacromolecule, cell migration, attach to titanium surface through having transformed, schizogamy, the synthetic cell epimatrix finally reaches organization healing, form good, stable titanium-organizational interface.The basic model at this interface is: titanio body-internal layer oxide-film is (with TiO
2Be main)-outer oxide film (being rich in hydroxyl or primary amino radical)-bioactive biomacromolecule-cell of tool.Therefore,, just can produce the biomacromolecule of biologically active, thereby form cell at inorganic material surface at inorganic material surface as long as the skin of the oxide-film of inorganic material surface is rich in hydroxyl or primary amino radical.This process is actually the process with inorganic material surface biological, but this process is very slow in vivo, thereby influences the process of organization healing.
The present invention by external to being coated with the inorganic material surface of titanium oxide or tantalum oxide thin film, carry out hydrogenation or ammonification with the plasma immersion ion injection device and handle and generate hydroxyl or primary amino radical organo-functional group; Further under the hydroxyl on inorganic bio surface, primary amino radical effect,, form firm chemical covalent bonds with the biomacromolecule-albumin or the heparin of biologically active, thereby in the external process of finishing inorganic material surface biological in advance.Its advantage is: the process of one, having accelerated the healing of the inorganic material artificial organ that implants and tissue.Two, inorganic material surface covalent bonds biomacromolecule, in conjunction with firm, adhesion is strong.Three, external during in conjunction with biomacromolecule, do not use chemical coupling agent, do not utilize static yet, do not damage biomolecule and proteic activity fully, prepared inorganic material surface has excellent anticoagulation function.Four, living hydroxyl of gas ions immersion ion injection and primary amino radical, immersion covalence graft biomacromolecule, can realize the complicated shape artificial organ is carried out comprehensive uniform surface biological modification, modification is even, stable, good reproducibility, also can guarantee simultaneously the mechanical performance and the corrosion resistance of material itself, be fit to industrial applications.
The present invention is further illustrated below in conjunction with accompanying drawing and concrete embodiment.
Description of drawings
The infrared light structure spectrogram that the material surface of inorganic material behind Fig. 1 sputter tantalum oxide thin film before and after plasma hydrogenation tested with Fourier transform infrared spectroscopy.Curve G wherein is the material surface infrared light structure spectrogram before the plasma hydrogenation; Curve H is the material surface infrared light structure spectrogram behind the plasma hydrogenation.
Fig. 2 a is SEM (scanning electron microscope) figure that the tantalum oxide film sample was tested in the Canis familiaris L. arterial blood body through 15 days.
Fig. 2 b is the SEM figure that plated film and the tantalum oxide film sample that forms hydroxyl through the plasma hydrogenation rear surface were tested in the Canis familiaris L. arterial blood body through 15 days.
Fig. 2 c is the SEM figure that the albuminous tantalum oxide film sample of surperficial Covalent Immobilization was tested in the Canis familiaris L. arterial blood body through 15 days.
The specific embodiment
Embodiment 1～8
These 8 embodiment plate tantalum-oxide film on inorganic material surface, generate hydroxyl again on tantalum-oxide film, last covalence graft albumin; All undertaken by following operating procedure:
A, sputter coating adopt existing non-balance magnetically controlled sputter technology, generate the tantalum oxide thin film in the inorganic material surface sputter.
Its concrete operations step is as follows:
Prepare the tantalum oxide thin film with the non-balance magnetically controlled sputter device.Present embodiment adopts existing non-balance magnetically controlled sputter device, comprising: workbench (sample platform), four sputtering target platform, pulse or dc source, workpiece, permutator, gas cylinder, grid bias power supply and heaters.
Clean: at first the metal tantalum target is contained on the target platform of non-balance magnetically controlled sputter equipment, workpiece is placed on the sample platform, closes vacuum chamber, is evacuated to 1 * 10
-3Handkerchief feeds argon, and the vacuum chamber argon pressure is opened the workpiece bias shielding power supply between 0.5～10 handkerchief, make argon ion glow discharge, and argon ion carries out sputter clean to workpiece, after 5～10 minutes, closes the workpiece bias shielding power supply.The vacuum chamber argon pressure remains between 0.5～10 handkerchief, utilizes the workpiece masking device to block workpiece, opens the target shielding power supply, make argon ion glow discharge, produce argon plasma in vacuum chamber, argon ion carries out sputter clean to metal targets, after 5～10 minutes, close target shielding power supply and argon.
Sputter forms the tantalum oxide thin film: open heating power supply, workpiece is heated to 20～400 ℃, feed argon and oxygen simultaneously, oxygen partial pressure is 0.1～5Pa, partial pressure of ar gas is 0.3～10Pa, open the workpiece masking device, make workpiece be exposed to target the place ahead, regulate target-substrate distance, open the target shielding power supply, load pulses negative voltage (regulating impulse supply frequency on sputtering target, dutycycle) or DC voltage, in vacuum chamber, form argon, oxygen plasma, under the negative voltage effect, argon ion bombardment metal tantalum target sputters tantalum atom and oxygen atom and is combined in surface of the work formation tantalum oxide thin film.In order to improve quality of forming film, in deposition process, open grid bias power supply, load pulses or dc negative bias voltage on workpiece.
The parameter of control film performance comprises: sputtering current 0.5～5 peace, sputtering time 5～120 minutes, oxygen pressure is 0.1～5Pa, argon pressure is 0.3～10Pa, sample platform Dc bias-300～-50 volts, sample heating-up temperature 20～500 degree, 50～200 millimeters of target-substrate distances, 10000～50000 hertz of pulse power frequencies.
In order to obtain the better tantalum oxide thin film of crystallization, also can carry out vacuum annealing to post-depositional tantalum oxide thin film and handle: the parameter that vacuum annealing is handled is a vacuum 3 * 10
-3～1 * 10
-4Handkerchief, annealing temperature 500～850 degree and annealing time 0.5～2 hour.
Technology and relevant parameter thereof that above non-balance magnetically controlled sputter generates the tantalum oxide thin film are prior art.
The generation of B, hydroxyl or primary amino radical: these 8 the equal using plasma immersion ion of embodiment injection devices have the workpiece of oxidation tantalum films to surface preparation, carry out plasma hydrogenation and handle, and form hydroxyl at inorganic material tantalum oxide film surface.
The operating procedure of 8 embodiment is: the inorganic material artificial organ after the A step is handled, put on the sample platform of plasma immersion ion injection device vacuum chamber, behind the evacuation, feed hydrogen or water vapour to vacuum chamber, open radio-frequency power supply, produce hydrogen plasma, open pulsed high voltage generator, under the effect of pulse negative high voltage, hydrion carries out omnibearing plasma hydrogenization to sample surfaces to be handled.8 pairing concrete plasma hydrogenization treatment process parameters of embodiment see Table 1.
The tantalum oxide thin film plasma hydrogenization treatment process parameter of table 1 embodiment 1～8
| Embodiment | Charge into the gas pressure (Pa) of vacuum chamber | Radio-frequency power (W) | Pulsed high voltage generator amplitude (KV) | Pulsed high-voltage source frequency (Hz) | Pulsed high-voltage source frequency dutycycle | Processing time (h) | The inorganic material heating-up temperature (℃) |
| 1 2 3 4 5 6 7 8 | 0.05 50 2 0.5 10 20 0.5 40 | 1200 600 200 800 100 700 300 1000 | 100 1 30 40 10 50 5 80 | 50 40000 200 100 20000 100 10000 50 | 3％ 80％ 10％ 8％ 30％ 3％ 20％ 5％ | 2 0.1 5 3 4 2.5 1 4 | 200 500 300 20 100 250 50 400 |
C, covalency connect the skill biomolecule: the inorganic material after the B step is handled, and to put into biological macromolecule solns and soak, the biological macromolecule solns of these 8 embodiment is specially albumin solution.During immersion, the parameter condition of each embodiment sees Table 2.
Technological parameter during table 2 embodiment 1～8 covalence graft
| Embodiment | Biological macromolecule solns concentration (mg/mL) | Soaking temperature (℃) | Soak time (h) |
| 1 2 3 4 5 6 7 8 | 10 60 50 30 100 55 10 80 | 20 30 40 40 40 30 20 25 | 48 5 10 2 48 20 2 30 |
Embodiment 1-8, be operating as more specifically during covalence graft: prepare albumin solution with distilled water earlier, add an amount of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), N-hydroxy-succinamide (NHS) and 2-morpholino b acid (MES) more successively, with activation albumin surface.Inorganic material after the B step processing is immersed rear enclosed in the albumin solution, place fixedly setting-up time of constant water bath box (can vibrate), take out.And remove the physical absorption layer of surface of the work through ultrasonic waves for cleaning after, seal up for safekeeping stand-by after the drying.
Embodiment 9-16
Embodiment 9-16 and embodiment 1-8 are corresponding identical respectively, different only be: in the step, the target that uses during sputter coating is Titanium at A, thus at inorganic material surface formation thin film of titanium oxide.
Embodiment 17-24
Embodiment 17-24 and embodiment 1-8 are corresponding identical respectively, different only be: B goes on foot the generation of hydroxyl or primary amino radical, generation be primary amino radical rather than hydroxyl.The gas that charges in the corresponding plasma immersion ion injection device vacuum chamber is ammonia.
Embodiment 25-32
Embodiment 25-32 and embodiment 1-8 are corresponding identical respectively, different only be following 2 points:
One, in A went on foot, the target that uses during sputter coating was Titanium, thereby formed thin film of titanium oxide at inorganic material surface.Two, the generation of B step hydroxyl or primary amino radical, generation be primary amino radical rather than hydroxyl.The gas that charges in the corresponding plasma immersion ion injection device vacuum chamber is ammonia.
Embodiment 33-40
Embodiment 33-40 is corresponding identical with embodiment 1-8, different only be: in the step, biological macromolecule solns is heparin solution rather than albumin solution at C.
Embodiment 41-48
Embodiment 41-48 is corresponding identical with embodiment 1-8, different only be following 2 points:
One, in A went on foot, the target that uses during sputter coating was Titanium, thereby formed thin film of titanium oxide at inorganic material surface.Two, the biological macromolecule solns of preparation was heparin solution rather than albumin solution during C went on foot.
Experiment and test proof, the inorganic material surface performance after the present invention handles is significantly improved.
Fig. 1 is the infrared light structure spectrogram of the forward and backward inorganic material surface of plated film post plasma hydrogenation with the Fourier transform infrared spectroscopy test, and wherein curve G is the infrared light structure spectrogram before the hydrogenation, and curve H is the infrared light structure spectrogram after the hydrogenation.As can be seen from Figure 1, curve H is at 3650cm
-1The characteristic absorption peak of tangible hydroxyl has appearred in the vicinity, and curve G does not then have corresponding absworption peak, show plasma hydrogenation after, inorganic material surface has newly formed hydroxyl.
Zoopery also proves the inorganic material behind the biology after the inventive method is handled, has shown the more excellent anticoagulation function and the ability of anti-hamartoplasia.
The method of experiment is: will only go on foot the inorganic material of processing (sputter tantalum-oxide film), go on foot the inorganic material of handling (sputter tantalum oxide thin film and plasma hydrogenation) through A, B through A, the inorganic material of the bioid that after A, B, three steps of C handle, obtains, three kinds of inorganic material samples are inserted the arteries inwall of Canis familiaris L., take out sample after 15 days and observe, the result of scanning electron microscope is respectively Fig. 2 a, Fig. 2 b, Fig. 2 c.
As can be seen from the figure, three kinds of samples all do not produce thrombosis, but first kind of sample surfaces produced some hamartoplasia things, and back two kinds of sample surfaces smoother are smooth, and the third is that sample surfaces behind the bioid is Paint Gloss smooth.
Claims (2)
1. the method for an inorganic material surface biological the steps include:
A, sputter coating: generate tantalum oxide or thin film of titanium oxide in the inorganic material surface sputter;
The generation of B, hydroxyl or primary amino radical:
Inorganic material after A step handled places on the sample platform of vacuum chamber of plasma immersion ion injection device, behind the evacuation, feeds hydrogen or water vapour, and pressure is 0.05～50 handkerchief; Radio-frequency discharge power is 200～1200W; Inorganic material loading pulse high voltage power supply amplitude is 1KV～100KV, 50～40000 hertz of frequencies, dutycycle 3%～80%; Inorganic material heating-up temperature 20～500 degree; In 0.1～5 hour processing time, promptly generate hydroxyl at inorganic material surface;
Inorganic material after perhaps A step being handled places on the sample platform of vacuum chamber of plasma immersion ion injection device, behind the evacuation, feeds ammonia, and pressure is 0.05～50 handkerchief; Radio-frequency discharge power is 200～1200W; Inorganic material loading pulse high voltage power supply amplitude is 1KV～100KV, 50～40000 hertz of frequencies, dutycycle 3%～80%, and inorganic material heating-up temperature 20～500 degree in 0.1～5 hour processing time, promptly generate primary amino radical at inorganic material surface;
C, covalence graft biomolecule: the inorganic material after B step handled, put into albumin or heparin solution soaks, the concentration of albumin or heparin solution is 10～100mg/mL, 20～40 ℃ of soaking temperatures, 2～48 hours time.
2. the method for a kind of inorganic material surface biological as claimed in claim 1 is characterized in that, when described B goes on foot the generation of hydroxyl or primary amino radical:
The pressure that feeds hydrogen or water vapour is 0.5～40 handkerchief; Radio-frequency discharge power is 300～1000W; Inorganic material loading pulse high voltage power supply amplitude is 5KV～80KV, 50～10000 hertz of frequencies, dutycycle 3%～20%; Inorganic material heating-up temperature 50～400 degree; 1～4 hour processing time;
The pressure that feeds ammonia is 0.5～40 handkerchief; Radio-frequency discharge power is 300～1000W; Inorganic material loading pulse high voltage power supply amplitude is 5KV～80KV, 50～10000 hertz of frequencies, dutycycle 3%～20%; Inorganic material heating-up temperature 50～400 degree; 1～4 hour processing time.
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